Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/38—Electroplating: Baths therefor from solutions of copper
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
  • C08G12/40—Chemically modified polycondensates
  • C08G12/42—Chemically modified polycondensates by etherifying
  • C08G12/421—Chemically modified polycondensates by etherifying of polycondensates based on acyclic or carbocyclic compounds
  • C08G12/422—Chemically modified polycondensates by etherifying of polycondensates based on acyclic or carbocyclic compounds based on urea or thiourea

Definitions

• the present invention relates in general to electrolytic acid solutions intended for depositing plain and bright copper films and has specific reference to the improvement in the electrolytic deposition from acid aqueous solutions of copper salts.
• organic addition compounds which meet the desired levelling and brightening requirements; these are thiophosphoric acid compounds heterocyclic sulfur compounds thiourea substitution compounds mercuric salts of triaryl-methanes dyes of the methylene blue group.
• the acid copper-plating solution according to this invention is characterized in that the surface brightening and levelling organic additives incorporated therein are both derivated from a resin resulting from the condensation of two formaldehyde moles over one thiourea mole, the product thus obtained being subsequently modified by a molecule having the general formula HA-R wherein A is a sulfur or oxygen atom R is an aliphatic, aromatic or cyclic radical.
• the difference between the brightening additive and the levelling additive lies chiefly in their degree of condensation, which is of the order of 300 to 600 for the former and of the order of 1,500 to 2,000 for the latter.
• the additives to be incorporated in the solution according to this invention are therefore derived from thiourea-formaldehyde resin by modifying same with the assistance of organic products having at least one OH and/or SH function which, by etherification or thioctherification of one OH function of the thio-ureaformaldehyde resin, create an O or S bridging attended by the elimination of one mole of water.
• the HA-R agents utilized for modifying the thioureaformaldehyde resin are selected from the groups comprising 1. Heavy aliphatic alcohols butanol, pentanol, hexanol, etc 2. aromatic or cyclic alcohols: phenol, benzylalcohol, cyclohexanol, etc 3. glycol esters glycol phthalate, etc 4. Aliphatic and aromatic thio-alcohols thiobutanol, thiophenol, etc 5.
• the temperature is kept at C the water distillates off slowly by azeotropy the condensation of organic compound molecules takes place and continues during a period of l to 3 hours respectively, according as it is desired to obtain a brightening agent (lower degree of condensation n, of the order of 500) or a levelling agent (higher degree of condensation n, of the order of 1,500).
• the resulting resin acting as a levelling or brightening agent is dissolved in 30 percent (by volume) sulfuric acid solution, in order to subsequently add same to the electrolytic acid copper plating solution containing furthermore one or a plurality of copper salts (such as sulfate), a small amount of Cl ions in the form of hydrochloric acid and a surface-active agent.
• sulfuric acid solution containing furthermore one or a plurality of copper salts (such as sulfate), a small amount of Cl ions in the form of hydrochloric acid and a surface-active agent.
• the deposit obtained from the above-described copper-plating solutions are extremely bright with current densities ranging from 0.1 to 20 Amp./sq.dm and are levelled with current densities ranging from 0.3 to 20 Amp./sq.dm.
• They can be nickel-plated directly without requiring any preliminary depassivation step.
• Aqueous acid electrolytic copper-plating solution containing at least one copper salt, a surface-active agent and organic additives adapted to promote a bright and levelled metal deposit, said organic additives having the formula:
• R designates an aliphatic radical having up to about 6 carbon atoms, cyclohexyl, phenyl, benzyl, diethylenethiourea and dimethylene phthalate, producing:
• a brightening agent wherein the organic additive has a condensation degree of about 300 to 600, or
• a levelling agent wherein the organic additive has a condensation degree of about 1,500 to 2,000.
• Acid electrolytic copper-plating solution according to claim 1 characterized in that the HA--- function of compound HA-R partakes in the creation of an ether or thioether linkage by becoming fixed to an OH function of the thiourea-formaldehyde molecule, with the elimination of one water molecule.
• Acid electrolytic copper-plating solution according to claim 2 characterized in that the compound modifying the thiourea-formaldehyde resulting product is an aliphatic alcohol having up to about 6 carbon atoms.
• Acid electrolytic copper-plating solution according to claim 2 characterized in that the compound modifying the thiourea-formaldehyde resulting product is phenol or benzyl alcohol.
• Acid electrolytic copper-plating solution according to claim 2 characterized in that the compound modifying the thiourea-formaldehyde resulting product is diglycol phthalate.
• Acid electrolytic copper-plating solution according to claim 2 characterized in that the compound modifying the thiourea-formaldehyde resulting product is an aliphatic thio-alcohol having up to 6 carbon atoms.
• Acid electrolytic copper-plating solution according to claim 2 characterized in that the compound modifying the thiourea-formaldehyde resulting product is thiophenol or thiobenzl alcohol.
• Acid electrolytic copper-plating solution according to claim 2 characterized in that the compound modifying the thiourea-formaldehyde resin is diethanol thiourea.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Electroplating And Plating Baths Therefor (AREA)
• Chemically Coating (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=9053208

Family Applications (1)

Country Status (5)

Cited By (2)

Citations (1)

• 1970
  • 1970-04-01 FR FR7011656A patent/FR2085243A1/fr not_active Withdrawn
• 1971
  • 1971-03-01 BE BE763626A patent/BE763626A/fr unknown
  • 1971-03-16 US US00124950A patent/US3770597A/en not_active Expired - Lifetime
  • 1971-03-31 CA CA109,281A patent/CA978892A/en not_active Expired
  • 1971-04-19 GB GB2452471*A patent/GB1337848A/en not_active Expired

Patent Citations (1)

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